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By J. L. Rodda

A large amount of time has been devoted to the microscopical study of the copper-zinc alloys, emphasis naturally being placed upon the commercially important alloys of the system. Suitable methods are available for microscopically recognizing the two phases richest in copper, but none appear to have been developed for the positive identification of the other phases. This is, however, accomplished, for the phases normally encountered, by an electrolytic method described in the following pages. Five phases of the copper-zinc diagram (Fig. I) are considered for the purpose of this paper: the solid solution of zinc in copper, alpha (a); the intermediate phases, beta (ß), gamma (?), and epsilon (e); and the solid solution of copper in zinc, eta (11). Beta prime is not considered a separate

Jan 1, 1937

By N. S. Stoloff, R. G. Davies

A study has been made of the efject oj different dislocation-precipitate interactions upon the temperature dependence of the flow stress of aged Ni-14 at. pct A1 alloy. It is observed that when the dislocations bow between widely spaced (-20004 coherent Ni3Al particles the flow stress decreases with increasing temperature in the normal way. However, when the dislocations cut closely spaced (-5004 particles the flow stress is independent of temperature from -100 to 600°C, due to a balance between softening of the matrix and an increase in strength of the particles with increasing temperature. The retention of strength at high tempera-tures of commercial nickel-base alloys, which are strengthened by the precipitation of a phase based upon Ni3Al, is thought to be due to the unusual strength properties of Ni3Al. The flow stress of Ni3Al increases continuous1y from -196"C to a maximum at -600"C. It is concluded from a series of thermal-mechanical tests that the sevenfold increase in flow stress over this temperature interval is due to a lattice effect and is not diffusion-controlled. The flow stress of precipitation- or dispersion-hardened materials depends on the resistance to dislocation motion within the matrix and the extra energy required for dislocations to bow between or to cut particles. If the dislocations bow between the particles or if the strength of the cut particles is constant with temperature, then the flow stress of the precipitation-hardened alloy must decrease with increasing temperature due at least to the decrease in elastic modulus of the material. There will be softening also from thermally activated cross-slip or climb, offering an additional degree of freedom for dislocations to avoid particles. For example, in the case of nickel containing a dispersion of thoria,' which most probably deforms by dislocations bowing between particles, the flow stress decreases by about 50 pct between 25" and 650°C. In A1-Cu alloys2 aged to produce the 8" precipitate, dislocations cut the particles, and the flow stress decreases by about 20 pct between -269" and 25°C. However, many commercial high-temperature nickel-base alloys, for example Inconel-X and Udimet-700, exhibit little or no decrease in flow stress with increasing temperature up to about 700°C. A characteristic feature of these alloys is that they are strengthened by the precipitation of a phase based upon Ni3A1. Guard and westbrook4 and flinn' have shown that Ni3Al (and alloys in which a third element such as molybdenum or iron is substituted for part of the aluminum) is unusual in that the hardness and flow stress increase with temperature to a maximum at about 600°C. For the flow stress of a precipitation-hardened alloy to be independent of temperature we propose that the particles must be cut by dislocations moving through the matrix and that the strength of the particle must increase with increasing temperature. Theories of precipitation hardening do not take into account the flow stress of the dispersed particles that are cut during deformation; the only dissipative process usually considered7 is the creation of interface within the particle and between the precipitate and matrix. The purpose of the present investigation has been to study in detail the temperature dependence of the flow stress of a nickel-base alloy strengthened by the precipitation of Ni3Al in two structural conditions such that when deformation occurs it does so by dislocations a) bowing between the particles and b) cutting the particles, respectively. A simple binary Ni-14 at. pct A1 alloy was chosen because considerable information is already available for this system concerning phase equilibria and precipitation reactions and rates.' Dislocation-precipitate interactions in the binary alloy should be similar to those in the more complex commercial alloys. In addition, the mechanical and physical properties of NisAl were studied in detail in the hope of elucidating the mechanism by which the strength increases with increasing temperature up to 600°C. EXPERIMENTAL PROCEDURE For the study of the effect of precipitation of Ni3A1 upon the temperature dependence of the flow stress, an alloy containing 14 at. pct A1 was utilized; a Ni-8 at. pct A1 solid-solution alloy was employed as a comparison material. Vacuum-cast ingots were hot-rolled at 1000°C and cylindrical compression samples, 0.20 in. diam by 0.40 in. high, were prepared from the 1/4-in.-diam rod. Specimens were recrystallized and solution-treated at 1000°C for 1/2 hr and then water-quenched. A preliminary study revealed that, when the Ni-14 at. pct A1 alloy was aged for 1 hr at 700°C, significant precipitation hardening was obtained, and that the structure was free from grain boundary discontinuous precipitation; an overaged condition was produced by annealing the aged specimens at 850°C for 1 hr. To circumvent the difficulties involved in the hot rolling and swaging of Ni3A1, compression samples,

Jan 1, 1965

By F. M. Stewart, F. H. Callaway, R. E. Gladfelter

In this paper oil initially in place is calculated by the various methods commonly used for analysis of water drive fields using data available as time progresses. Rate and pressure are predicted by means of the same methods using data available at the end of two years' history. These predictions are then compared with subsequent performance permitting an evaluation of the methods, which are Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer. INTRODUCTION Several variations of the material balance equation, differing in the term used to evaluate water influx, are in common use for estimating oil in place, predicting rate and volume of water influx, and forecasting producing rates and reservoir pressure in water drive reservoirs. The electric analyzer with an electrical network set up to simulate the oil reservoir and aquifer and their contained fluids may be used for the same purpose. Examples of the application of one or another of these methods have appeared in the literature. The accuracy and reliability of the material balance for calculating oil in place have been covered.' However, there have been few articles in which more than one method has been applied to an actual field allowing a comparison. It is felt that a field example, simple in nature, where the Modified Schilthuis, Simplified Hurst, van Everdingen et al (1952), and the Electric Analyzer have been applied would be of benefit in providing an evaluation of these methods as to their comparative usefulness and reliability in calculating initial oil in place and predicting performance. The Torchlight Tensleep reservoir is a small field in a large aquifer. The reservoir oil is greatly under-saturated, having a bubble point of only 55 psi and 2 cu ft/bbl of gas in solution. Changes in the reservoir volume factor in the range of pressures encountered are small, meaning little error in converting production to reservoir conditions. The pressure has declined from 1,618 psi initially to 137 psi during the first four and one-half years. Water production has been negligible. For Torchlight, the material balance equation as discussed later is considerably simplified by the omission of terms having to do with free gas. Thus with simpler equations, less variables to consider, the large pressure drop, the absence of a gas phase, and rapid pressure-rate adjustments, which mean an unusual amount of history in a short time, the reservoir appears suitable for comparing the methods listed above. GENERAL INFORMATION ON THE FIELD The Torchlight field is located on the eastern side of the Big Horn Basin, Big Horn County, Wyo., approximately 3 miles east of the town of Basin. The Tensleep reservoir was discovered in September, 1947. It lies at a depth of about 3,000 ft and produces oil of 35" API gravity. A total of five wells have been completed in the Tensleep, but only four are now producing. The reservoir is well defined in areal extent in that a total of 13 wells have penetrated the Ten-

Jan 1, 1955

By V. D. O’Leary

Progress in Butte has always been marked by changes which have not only altered the physical appearance of the city, but have also greatly affected the manner and means of mining. The innovation of the Berkeley pit is an example of the former, and the introduction of blockcaving at the Kelley mine is an example of the latter. Now the camp is on the brink of another change which won't be visible on surface but will have an important impact on future underground operations. This change is known as the Deep Level Plan and has been under study for the better part of five years. In this plan all ore from the deep level mines (Mountain Con, Steward, Leonard and Belmont) will be hauled on two haulage levels, at depth, to the Kelley mine and there hoisted to surface.

Jan 11, 1963

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

By F. Weinberg

The distribution of solute during the progressive solidification of dilute Sn-Ag alloys was determined in both solid and liquid as a jbnction of growth rate, rod diameter, temperature gradient, and solute concentration, using radioactive tracer techniques. The results indicated that partial mixing occurs in the liquid during freezing for most of the conditions investigated, approaching complete mixing for larger rod diameters (>2mm) and slow growth rates. Measured solute distributions were fitted to distribution functions based on diffusion controlled solute transport in the liquid state, by treating the normal solute diffusion constant and distribution coefficient as variable solute transport and segregation parameters. Values of these parameters were determined for the growth conditions investigated. Observations were made to determine whether mixing in the liquid was primarily due to volume changes in freezing or to differences in density between solute and solvent. The former effect was investigated using a selected Sn-Bi alloy as a solvent with zero volume change on fusion, and the density effect was studied using vertical solidifications of Sn-In and Sn-Ag alloys, systems having, respectively, very small and large differences in density between solute and solvent. The result indicate that mixing in the liquid cannot be primarily attributed to either volume changes or density differences. THE solute distribution in progressively solidified rods of dilute alloys, in which there is complete mixing in the liquid, is given by the expression1 where C, is the solute concentration in the solid at the point where the fraction g of the material has solidified, C, is the initial solute concentration and k is the equilibrium distribution coefficient. If it is assumed that there is no significant con-vective mixing in the liquid, then the solute distribution in the initial portion of a semi-infinite rod has been calculated to be2 where t is the time from the start of freezing and x1 is the distance in the liquid ahead of the solid-liquid interface at time t. Expressions [1] and [2] describe the limiting cases of solute distribution in the liquid, i.e., complete mixing, or no convective mixing; in practice it might be expected that the solute distribution would be somewhere between these two cases. pfann3 has suggested that Eq. [I] is applicable for partial mixing, as well as complete mixing, if an effective distribution coefficient k1 is used instead satisfactorily describes solute distributions in rods of magnesium, n-g, and b-sb6 alloys that were progressively solidified from the melt without mechanical mixing. The values of kl were observed to depend on the growth rate4-6 and the temperature gradient.6 The purpose of the present investigation was to measure solute distributions in both the solidified rods and the melt as a function of the solidification variables, and to determine to what extent the observed solute distributions could be described by the above theoretical expressions, keeping in mind that expressions [2] and [3] have been derived solely for the case of diffusion controlled solute transport in the liquid and are not theoretically applicable to

Jan 1, 1963

By J. D. Meakin

J. D. Meakin (The Franklin Institute Laboratories)— In a recent paper Garofalo12 has shown that a number of experimental creep results can be represented by the empirical relation In this expression ? is the steady creep rate, s is the applied stress, and A is a constant at a given temperature; a and n are adjustable parameters. Garofalo has shown that Expression [6] approximates to a power function at low stresses and a simple exponential function at high stresses. Among the data used by Garofalo are the results we published for creep of copper." For these results we found that the best correlation was an exponential law with different parameters in the low-and high-stress region, respectively. That is, i = A exp qs where A and q have different values above and below a critical stress a,. In Ref. 13 are listed a variety of observations which support the proposal that different mechanisms are operative at stresses above and below a,, and it is not felt appropriate to repeat those observations here. The purpose of this note is to demonstrate that, although the representation used by Garofalo does fit the experimental data very well, this fit cannot be used to conclude that only one mechanism is rate-controlling. The argument is best made graphically and is illustrated in Fig. 9. The continuous curves 2 and 3 represent pairs of simple exponential functions which intersect at i = 10-5. The curve 2 closely resembles the copper results in that a change of slope of 2:1 occurs at i = 10-5; the two functions shown are in fact: e = 10-7 exp (1.150) and ? = 10-6&apos; exp (0.576s) For purposes of comparison, curve 3 represents two exponential functions with a change of exponent of 3:1 and curve 1 has the exponent 1.150 throughout. It is quite clear that a satisfactory straight-line fit is obtained on a Garofalo plot for all three curves. The curves represent processes which have either a single stress exponent or two ex- ponents in a ratio as high as 3:l. It must, therefore, be concluded that the ability to obtain a linear dependence between log i and log (sinh cyo) cannot be taken as evidence for a single activated process. In fact, to some extent the way the experimental points quoted by Garofalo lie about a best fit straight line on the log (sinh as) plot indicates that two processes are indeed occurring. This is seen in Figs. 7(c) and 8(c) of Ref. 12 where it is particularly evident that the experimental points deviate from the straight line in a manner similar to curves 2 and 3 of Fig. 9. It is, of course, recognized that the generally used exponential form is an approximation to the hyperbolic sine function which is not valid for exponents of less than 1.2, e.g., qs < 1.2. The only curve in Ref. 12 which is affected by this restriction is Fig. 6(b) where the deviation from a In ? vs s

Jan 1, 1964

By C.R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I&apos; The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By C. R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I&apos; The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By L. J. Erck, T. E. Ban

A discussion of laboratory procedures used to determine pellet quality and to simulate handling and firing conditions. Strength-temperature relationships in pelletizing; effect of chemical additives on agglomeration; and crushing, abrasion, and impact resistance of the pelletized products are discussed with respect to five different iron ore concentrates. IN most routine experimental work on products and processes, method:; of operation and product evaluation are established from accurately controlled laboratory tests. With particular emphasis on the pelletization of fine iron ore concentrates, standardized procedures of laboratory production and product testing have been established at Cleveland-Cliffs Iron Co. Research Laboratory at Ishpeming, Mich. A program of this nature was used for investigating the agglomeration characteristics of various iron ore concentrates. The factors which control the process were studied and subsequently controlled for these investigations. Pelletizing as applied to iron ore agglomeration involves the preparation of spheroidal masses from a fine moist concentrate, followed by high-tempera-ture firing to produce a final product. The preparation of moist spherorids is generally designated as balling. This produces the so-called green pellets or balls. After, these have been fired they are called pellets. Balling is accomplished by rolling moist concentrates in a revolving drum until small spheroids form by a snow-balling action. These balls are then heated in a shaft furnace, or a modification of this device, to a temperature high enough to cause agglomeration within the individual balls while they descend countercurrent to hot oxidizing gases. By this process the lour strength balls are converted through various chemical and physical-chemical processes into hard pellets. With correct balling and firing, the pellets are strong, resist abrasive action and handling treatments, and provide a suitable blast furnace and open hearth feed. In 1950 Tigerschiold and Ilmoni developed a working hypothesis to explain the formation and stability of green pellets.&apos; Their work was presented on the basis of geologists&apos; discoveries concerning the soil-water system and C. V. Firth&apos;s early postulates of green pellet formation.&apos; Fundamental reactions oc-curing within fired pellets have been described by Cooke and Ban, who showed the microstructure changes caused by different firing temperatures." All these investigators have provided scientific clarifications of agglomeration by the pelletizing process and have opened avenues for greater development. Mineral grain growth and ceramic bond formation are the two basic phenomena imparting coherency to particles within a fired pellet of iron ore. Each of these is established by the transfer of thermal energy to the mineral particles. Grain growth mechanisms are chiefly physical reactions wherein smaller particles consolidate into larger ones, with resulting decrease in surface energy conforming with the second law of thermodynamics. Ceramic bond formation is a chemical reaction usually between basic and acid metallic oxides of the gangue and ore minerals. CaO, MgO, A1203, and FeO of Fe3O4, react in varying proportions with SiO, or Fe2O3, to form a great series of compounds or amorphous solid solutions. These product bond iron mineral particles together by a bridging action or by direct reaction with the surfaces of the particles. The result of the grain growth-ceramic bond formations is a consolidated, coherent compact of gangue and iron minerals formerly held together by much weaker bonds of interstitial water and forces common to dry, unconsolidated particles.4 With respect to iron ore agglomeration, these high temperature bonding reactions have been described by Schwartz, who referred to the bonds in sinters," and by Cooke and Ban, who referred to the bonds in fired pellets." The extent of the bonding phenomena and the consequent strength of fired pellets is governed by

Jan 1, 1954

By Thomas F. Bates

ANALYSIS of the chemical and structural differences in minerals often results in a better understanding of the differences in the geological conditions under which they were formed. The minerals in the kaolinite group differ in the amount of interlayer water and in the nature and amount of ordered and/or random shifting of each 1:1 layer with respect to those above and below it. This paper is a progress report resulting from research on the morphology, structure, and origin of fine-grained minerals, supported by Contract N6onr26914 with the Geophysics Branch of the Office of Naval Research. The purpose of the paper is to present data obtained in the laboratories at The Pennsylvania State College and elsewhere, which reveal some of the details of structure of the minerals in the kaolinite group, and to suggest a number of interpretations that bear upon the conditions of origin of these minerals. Be¬cause most of the work in this investigation thus far has been concerned with the relationships of kaolinite, halloysite (4H2O; endellite), and halloysite (2H2O), must of the discussion deals with these members of the group. The first step in the analysis of the differences in two sets of geological conditions is an evaluation of the differences in the minerals that result. Thus the chemical differences between the montmorillonite and the kaolinite clays corroborate other evidence in support of the view that the montmorillonites are commonly formed when solutions are alkaline and leaching poor, while kaolinite usually is associated with acid solutions and good drainage condi¬tions. It is obvious that the greater the differences in the minerals, the more divergent may be the conditions that give rise to them and the more readily one condition can be distinguished from the other. In the kaolinite group, differences between individual members are small, therefore the differences in condition of origin are presumably subtle and difficult to define. At the same time, the very fact that the minerals differ only slightly makes them more sensitive indicators of the exact conditions under which they and the minerals associated with them were formed. Since clay minerals are being used more and more to evaluate the nature, value, and mode of formation of economic mineral deposits, an attempt to define these subtle differences would appear worth while. For purposes of the present discussion, the minerals nacrite, dickite, kaolinite, the so-called "fireclay mineral," halloysite (4H2O), halloysite

Jan 1, 1952

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.&apos; and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~&apos; have reported the structure of

Jan 1, 1965

By J. P. Smith

Permian salt measures carry extensive lenses of soluble potash salts in north central Germany. Potash deposits of Oligocene age are found in the Upper Rhine Graben of Alsace (France), and in the Catalonian Basin of Spain. These deposits are found in a wide range of structural settings. Reserves are large, and the production of potash salts is an important phase in the economy of each of these countries.

Jan 1, 1950

By Herbert H. Uhlig

ALTHOUGH the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldlo summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.15 per cent carbon. He noted: From these comparisons it will be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable. Ib His data showed that alloys containing 4 to 10 per cent manganese water-quenched from 1000°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 870°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loringa reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 540°C. (1000°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.15 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <0.001 per cent P). In this paper it is shown that of the low- carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from 1000°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

Jan 1, 1946

By Paul Weir

Bleaching clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller&apos;s earths fall within the general group of bleaching clays and gradually the commercial term "fuller&apos;s earth" has been applied to natural clays originating, for the most part, in the southeastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.l Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). The fuller&apos;s earth type of clay is characterized by a lack of plasticity, relatively adsorbent, foliated structure, and does not swell to form a

Jan 1, 1942

By Paul Weir

Bleaching clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller&apos;s earths fall within the general group of bleaching clays and gradually the commercial term "fuller&apos;s earth" has been applied to natural clays originating, for the most part, in the southeastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.l Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). The fuller&apos;s earth type of clay is characterized by a lack of plasticity, relatively adsorbent, foliated structure, and does not swell to form a

Jan 1, 1942

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-&apos; the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:&apos; and, if some simplifying assumptions about particle shape are allowed, the total number of particles.&apos;2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.&apos; Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By H. E. Stauss, E. I. Salkovitz, F. W. von Batchelder

EXISTING information regarding the structure of a spherulite in nodular cast iron is based on optical studies. According to these data, a nodule consists of an aggregate of graphite crystallites radiating from the center, with the closely packed basal planes at right angles to the radii. The c axes lie along the radii. This view faces some uncertainty in the fact that the c axis does not represent the accepted direction of fastest growth in graphite. To supplement the optical information, X-ray studies have now been made. The principle used was to screen the nodule in greater part from the X-ray beam and expose only a minor cap. As successively larger portions of the nodule were introduced into the X-ray beam, any differences in the X-ray patterns could be observed. Such photographs have been taken with chromium radiation and a Laue camera. The graphite nodule itself, about 0.010 to 0.025 in. in diam, was mounted with vaseline on a micrometer screw for control of the linear motion. The nodule rotated about 45" each time that it was translated linearly. The nodules were obtained from magnesium-treated hypereutectic iron by electrolytic solution of the iron in hydrochloric acid. In Fig. la is shown the pattern of the thinnest cap examined. In Fig. lb is shown the pattern of the same nodule moved 0.003 in. farther into the X-ray beam, and rotated 45" at the same time. Figs, la and lb indicate incomplete circles for graphite (the two outer circles arise from graphite) with the side arcs much weaker than the top and bottom ones. The arcs obtained are themselves not continuous in intensity but vary with maxima of intensity some 15" and 30" apart. The structure of the nodule that would give rise to such a pattern can be explained as follows. Basically the nodule consisted of small crystallites. The discontinuous character of the diffraction rings demonstrates that the nodule was not composed of randomly oriented crystallites. The strong vertical reflections and the weak lateral reflections show that the reflecting planes were roughly normal to the radii. The absence of sharp reflection spots suggests that the nodule did not contain large crystals. The sharpness of the diffraction rings in their radial direction shows that the variations in intensity along the arcs were not the result of line broadening resulting from extremely small crystals. In the diffraction patterns two rings corresponding to graphite were found. The third and inner ring in the figures originated in the vaseline. The graphite rings correspond to the a and ß lines reflected from the basal planes, showing that the radii of the nodules are the [0001] direction normal to the basal planes of graphite. The picture of the structure that is formed is, therefore, one of aggregates of crystallites. Within each aggregate the c axes of the crystallites tend to align themselves in the radial direction of the nodule, although these axes deviate somewhat in direction by a continuous variation of angle. Correspondingly the basal planes of the graphite crystallites are generally normal to the radii. It is a pleasure to acknowledge the assistance of M. C. Bloom and R. P. Dunphy of this laboratory.

Jan 1, 1952